Meta-bis anilide derivatives and their utility as herbicides

ABSTRACT

Compounds corresponding to the formula: ##STR1## in which R 1  and R 2  are, independently, hydrogen, alkyl, alkoxyalkyl, cycloalkyl, pinonyl, ethylcycloalkyl, lower alkenyl, halogenated lower alkyl, benzyl, ethylphenyl, 2,4-dichlorophenoxy-methylene, styryl, furyl, phenyl or substituted phenyl in which the substituents are nitro, halogen, methyl, or methoxy; R 3  and R 4  are, independently, hydrogen or lower alkyl; X and Y are independently oxygen or sulfur; and Z is halogen, nitro, amino, lower alkyl, lower alkoxy or trifluoromethyl and n is an integer having a value from 0 to 4. The above compounds are effective herbicides, particularly for the control of grasses and broadleaf plants with both pre-emergence and post-emergence activity. Representative compounds are: m-propionamidobutyranilide, m-bis-2,2-dimethylvaleranilide, m-isobutyramido trichloroacetanilide, m-isobutyramido-2-ethylbutyranilide, m-t-butylacetamido-propionanilide, and 3&#39;-N-ethyl propionamido-propionailide.

This application is a divisional application of Ser. No. 179,224 filed Sept. 9, 1971, now U.S. Pat. No. 3,941,581, issued Mar. 2, 1976, which in turn was a division of then copending Ser. No. 20,104, filed Mar. 16, 1970, now abandoned, which was a continuation-in-part of then copending Ser. No. 741,267 filed July 1, 1968, now abandoned, which was a continuation-in-part of then copending application Ser. No. 659,865, filed Aug. 11, 1967, now abandoned.

This invention relates to herbicidally active meta-bis anilide derivatives. More specifically, this invention relates to certain new compounds and the use as active herbicidal substances of certain substituted meta-bis-anilides.

The novel compounds of the present invention correspond to the general formula: ##STR2## in which R₁ and R₂ are independently selected from the group consisting of hydrogen, alkyl, alkoxyalkyl, cycloalkyl, pinonoyl, ethylcycloalkyl, lower alkenyl, halogenated lower alkyl, benzyl, furyl, ethylphenyl, 2,4-dichlorophenoxy-methylene, styryl, phenyl, and substituted-phenyl in which said substituents are nitro, halogen, methyl or methoxy; selected from the group consisting of hydrogen and lower alkyl; X and Y are independently oxygen or sulfur; and Z is selected from the group consisting of halogen, nitro, amino, lower alkyl, lower alkoxy, and trifluoromethyl and n is an integer having a value from 0 to 4.

The method of the present invention of controlling undesirable vegetation comprises applying an herbicidally effective amount of the above represented compounds to the area where control is desired. Compounds wherein R₁ and R₂ are independently selected from the group consisting of alkyl, hydrogen, alkoxyalkyl, cycloalkyl, pinonoyl, ethylcycloalkyl, lower alkenyl, halogenated lower alkyl, benzyl, 2,4-dichlorophenoxymethylene, styryl, phenyl, phenyl and substituted phenyl in which the substituents are nitro, halogen, methyl or methoxy; R₃ and R₄ are independently selected from the group consisting of hydrogen and lower alkyl; X and Y are independently oxygen or sulfur; and Z is selected from the group consisting of halogen, nitro, amino, lower alkyl, lower alkoxy, and trifluoromethyl and n is an integer having a value from 0 to 4; are within the scope of this aspect of the present invention.

The term alkyl, preferably includes those members of the group which contains from 1 through about 10 carbon atoms, inclusive, in both straight chain and branched chain configurations. The term lower alkyl and lower alkoxy preferably include members of the groups having from 1 through about 6 carbon atoms, inclusive. The term alkoxyalkyl includes members having 2 to 4 carbon atoms. The term cycloalkyl preferably includes members of the group having from 3 through about 6 carbon atoms, inclusive. The term lower alkenyl preferably includes those members of the group containing at least one double bond and containing from 2 to 4 carbon atoms, inclusive.

In its most preferred form, the invention relates to compositions having the formula ##STR3## in which R₁ and R₂ independently are hydrogen, alkyl containing from 1 to 10 carbon atoms, inclusive, alkoxyalkyl containing 2 to 4 carbon atoms, cycloalkyl containing from 3 to 6 carbon atoms, inclusive, pinonoyl, ethylcycloalkyl wherein the cycloalkyl moiety contains from 5 to 6 carbon atoms, inclusive, lower alkenyl containing from 2 to 6 carbon atoms, inclusive, halogenated lower alkyl containing 1 to 6 carbon atoms, inclusive, benzyl, furyl, ethylphenyl, styryl, 2,4-dichlorophenoxy-methylene, phenyl and substituted phenyl in which said substituents are nitro, halogen, especially chlorine and fluorine, methyl, and methoxy; and Z is hydrogen, 4'-chloro, 3'-chloro or 2'-methyl.

The compounds of this invention are prepared by one of several general methods. One such general method is the condensation between the appropriate m-phenylene diamine and an appropriate acid anhydride or chloride to prepare the desired meta-bis-symmetrically substituted anilide. Another general method is the condensation between the appropriate m-mono-substituted amino anilide and an appropriate acid anhydride or acid chloride to prepare the desired meta-bis-assymetrically substituted anilide. The reactions proceed readily in the liquid phase. The employment of a solvent is also useful, facilitating processing, as well as agitation of the reactants. When using a starting material containing an acid chloride, it is preferred to carry out the reaction in the presence of a hydrogen halide acceptor such as triethylamine, pyridine, picoline, sodium carbonate and the like. The reactions are preferably carried out at temperatures that permit operation in the liquid phase.

Compounds of the present invention are prepared in accordance with the following illustrative examples.

EXAMPLE 1 Preparation of Meta-bis-isobutyranilide.

Isobutyric anhydride, 26 g. (0.16 mole) is added slowly to 8.6 g. (0.08 mole) of m-phenylene diamine in an open beaker. The mixture was stirred. The solid product is washed consecutively with water, sodium bicarbonate solution and ether. After drying, there is obtained 18.5 g. (92 percent of theory) of the title compound, m.p. 205°-206° C.

The following compounds are typical of those prepared using the method of the foregoing example: m-bis-acetanilide, m-bis-propionanilide, m-bis-n-butyranilide and m-bis-trifluoroacetanilide.

EXAMPLE 2 Preparation of Meta-bis-2,2-dimethyl-valeranilide.

Meta-phenylene diamine, 87 g. (0.8 moles), is dissolved in one liter of acetone containing 190g. (1,9 moles) of triethylamine. To this solution, 2,2-dimethylvaleryl chloride, 260 g. (1.75 moles) is added slowly with stirring. The reaction flask is cooled in a cold water bath. The resulting mixture is poured into 1-liter of cold water and the resulting oil crystallized. The product is further washed with water, then 5 percent hydrochloric acid solution, followed by 5 percent sodium hydroxide solution and finally water. The product is dried. There is obtained 256 g. (96 percent of theory) of the title compound, m.p. 109°-111° C.

The following compounds are typical of those prepared using the method of the foregoing example: m-bis-pivalanilide, m-bis-3,3-dimethylbutyranilide, m-bis-crotonanilide, m-bis-hexanilide, and m-bis-isovalerylanilide.

EXAMPLE 3 Preparation of Meta-propionamido isobutyranilide.

Meta-amino propionanilide, 11.5 g. (0.07 moles) is treated with isobutyric anhydride, 11.1g. (0.07 moles) is an open beaker. The product is poured into water and washed with 5 percent hydrochloric acid solution, 5 percent sodium hydroxide solution, and water. The product is dried of water. There is obtained 15.2 g. (93 percent of theory) of the title compound, m.p. 174°-175° C.

The following compounds are typical of those prepared using the method of the foregoing example: m-propionamido trifluoroacetanilide, m-propionamido butyranilide, m-isobutyramido trifluoroacetanilide and m-isobutyramido butyranilide.

EXAMPLE 4 Preparation of Meta-propionamido cyclopropane carboxanilide.

Meta-aminopropionanilide, 13.1 g. (0.08 mole) is dissolved in 200 ml. of a 50/50 v/v mixture of glacial acetic acid and saturated sodium acetate solution. To this solution is added 9.2 g. (0.088 moles) of cyclopropane carbonyl chloride. The chloride is added slowly with adequate stirring and cooling. The product, which crystallizes from the solution, is collected by filtration. The product is consecutively washed with a 5 percent solution of sodium hydroxide, a 5 percent solution of hydrochloric acid and water. After washing, the crystals are dried. There is obtained 15 g. (81 percent of theory) of the title compound, m.p. 185°-186° C.

The following compounds are typical of those prepared using the method of the foregoing example: m-propionamido cyclohexanecarboxanilide, m-propionamido phenyl-acetanilide, m-propionamido crotonanilide, and m-propionamido furoanilide.

EXAMPLE 5 Preparation of Meta-propionamido-3,3-dimethyl butylanilide.

Meta-aminopropionanilide, 180 g. (1.1 moles) is dissolved in 500 ml. of acetone containing 126 g. of triethylamine. To this solution is added 164 g. (1.22 moles) of 3,3-dimethyl butyryl chloride. The chloride is added slowly and the reaction mixture is adequately stirred and cooled, with an ice bath. The mixture is poured into water and consecutively washed with 5 percent hydrochloric acid solution, 5 percent sodium hydroxide solution, and water. After washing, the material is dried. There is obtained 178 g. (62 percent of theory) of the title compound, m.p. 179.5° - 181.5° C.

The following compounds are typical of those prepared using the method of the foregoing example: m-propionamido-2,2-dimethyl valeranilide, m-propionamido-2 ethyl butyranilide, m-propionamido pivalanilide, and m-pivalamino-2-2-dimethyl valeranilide.

The following is a table of the compounds which are prepared according to the aforedescribed procedures. Compound numbers have been assigned to them and are used for identification throughout the balance of the specification.

                                      TABLE I                                      __________________________________________________________________________      ##STR4##                                                                      Com-                                                                           pound                                                                          Number                                                                              X Y R.sub.1      R.sub.2     R.sub.3                                                                            R.sub.4                                                                          Z    m.p. ° C.                  __________________________________________________________________________     1    0 0 C.sub.2 H.sub.5                                                                             C.sub.2 H.sub.5                                                                            H   H      174-175                           2    0 0 furyl        furyl       H   H      191-194                           3    0 0 CH.sub.3     CH.sub.3    H   H      186-188                           4    0 0 CH.sub.3     C.sub.2 H.sub.5                                                                            H   H      239-243                           5    0 0 CH.sub.3     i-C.sub.3 H.sub.7                                                                          H   H      165-167                           6    0 0 n-C.sub.3 H.sub.7                                                                           n-C.sub.3 H.sub.7                                                                          H   H      142.5-143                         7    0 0 i-C.sub.3 H.sub.7                                                                           i-C.sub.3 H.sub.7                                                                          H   H      205-206                           8    0 0 C.sub.2 H.sub.5                                                                             CCl.sub.3   H   H      159-161                           9    0 0 H            H           H   H      152- 154                          10   0 0 C.sub.2 H.sub.5                                                                             CH.sub.2 Cl H   H      164-167                           11   0 0 C.sub.2 H.sub.5                                                                             CF.sub.3    H   H      196-197                           12   0 0 C.sub.2 H.sub.5                                                                             C.sub.3 H.sub.7                                                                            H   H      156-157                           13   0 0 C.sub.2 H.sub.5                                                                             i-C.sub.3 H.sub.7                                                                          H   H      174-175.5                         14   0 0 C.sub.2 H.sub.5                                                                             cyclopropyl H   H      186-188                           15   0 0 C.sub.2 H.sub.5                                                                             i-C.sub.4 H.sub.9                                                                          H   H      130-131                           16   0 0 C.sub.2 H.sub.5                                                                             n-C.sub.5 H.sub.11                                                                         H   H      173-178                           17   0 0 CH.sub.2 Cl  CH.sub.2 Cl H   H      211-212                           18   0 0 CHCl.sub.2   CHCl.sub.2  H   H      158-160                           19   0 0 CH.sub.2 CH.sub.2 Cl                                                                        CH.sub.2 CH.sub.2 Cl                                                                       H   H      160-163                           20   0 0 CHCH.sub.2   CHCH.sub.2  H   H      167-170                           21   0 0 CHCHCH.sub.3 CHCHCH.sub.3                                                                               H   H      215-217.5                         22   0 0 cyclopropyl  cyclopropyl H   H      217-221                           23   0 0 i-C.sub.4 H.sub.9                                                                           i-C.sub.4 H.sub.9                                                                          H   H      226-230                           24   0 0 n-C.sub.5 H.sub.11                                                                          n-C.sub.5 H.sub.11                                                                         H   H      122-125                           25   0 0 n-C.sub.6 H.sub.13                                                                          n-C.sub.6 H.sub.13                                                                         H   H      109-113                           26   0 0 cyclohexyl   cyclohexyl  H   H      210-212.5                         27   0 0 benzyl       benzyl      H   H      194-197                           28   0 0 CCl.sub.3    CCl.sub.3   H   H      204-207                           29   0 0 C(CH.sub.3).sub.2 Br                                                                        C(CH.sub.3).sub.2 Br                                                                       H   H      126-128                           30   0 0 t-C.sub.4 H.sub.9                                                                           t-C.sub.4 H.sub.9                                                                          H   H      188-189                           31   0 0 CH(C.sub.2 H.sub.5).sub.2                                                                   CH(C.sub.2 H.sub.5).sub.2                                                                  H   H      148-151                           32   0 0 phenyl       phenyl      H   H      234-237.5                         33   0 0 3-NO.sub.2 -phenyl                                                                          3-NO.sub.2 -phenyl                                                                         H   H      250-255                           34   0 0 C.sub.2 H.sub.5                                                                             CHCl.sub.2  H   H      159-163                           35   0 0 CHCH.sub.2   C.sub.2 H.sub.5                                                                            H   H      165-166.5                         36   0 0 C.sub.2 H.sub.5                                                                             CH.sub.2 CH.sub.2 Cl                                                                       H   H      139-142                           37   0 0 C.sub.2 H.sub.5                                                                             CHCHCH.sub.3                                                                               H   H      183-186                           38   0 0 C.sub.2 H.sub.5                                                                             C(CH.sub.3).sub.2 Br                                                                       H   H      165-167                           39   0 0 C.sub.2 H.sub.5                                                                             n-C.sub.6 H.sub.13                                                                         H   H      256-260                           40   0 0 C.sub.2 H.sub.5                                                                             furyl       H   H      151-152.5                         41   0 0 C.sub.2 H.sub.5                                                                             cyclohexyl  H   H      300-304                           42   0 0 C.sub.2 H.sub.5                                                                             phenyl      H   H      210-213                           43   0 0 C.sub.2 H.sub.5                                                                             3-NO.sub.2 -phenyl                                                                         H   H      198-201                           44   0 0 C.sub.2 H.sub.5                                                                             benzyl      H   H      129-130                           45   0 0 i-C.sub.3 H.sub.7                                                                           cyclopropyl H   H      184-187                           46   0 0 i-C.sub.3 H.sub.7                                                                           CHCH.sub.2  H   H      186-190                           47   0 0 i-C.sub.3 H.sub.7                                                                           n-C.sub.4 H.sub.9                                                                          H   H      124-126                           48   0 0 i-C.sub.3 H.sub.7                                                                           i-C.sub.4 H.sub.9                                                                          H   H      141-143                           49   0 0 i-C.sub.3 H.sub.7                                                                           furyl       H   H      152-154                           50   0 0 i-C.sub.3 H.sub.7                                                                           cyclohexyl  H   H      142-145                           51   0 0 i-C.sub.3 H.sub. 7                                                                          phenyl      H   H      152-153                           52   0 0 i-C.sub.3 H.sub.7                                                                           3-NO.sub.2 -phenyl                                                                         H   H      156-161                           53   0 0 CHClCH.sub.3 CHClCH.sub.3                                                                               H   H      169.5-173                         54   0 0 C(CH.sub.3)CH.sub.2                                                                         C(CH.sub.3)CH.sub.2                                                                        H   H      139-141                           55   0 0 C(CH.sub.3).sub.2 C.sub.3 H.sub.7                                                           C(CH.sub.3).sub.2 C.sub.3 H.sub.7                                                          H   H      96-100                            56   0 0 CHClCH.sub.3 C.sub.2 H.sub.5                                                                            H   H      164-166                           57   0 0 C.sub.2 H.sub.5                                                                             C(CH.sub.3)CH.sub.2                                                                        H   H      154-157                           58   0 0 i-C.sub.3 H.sub.7                                                                           CH.sub.2 Cl H   H      205-209                           59   0 0 i-C.sub.3 H.sub.7                                                                           CHCl.sub.2  H   H      178-180.5                         60   0 0 i-C.sub.3 H.sub.7                                                                           CCl.sub.3   H   H      160-162                           61   0 0 i-C.sub.3 H.sub.7                                                                           CHClCH.sub.3                                                                               H   H      168-172                           62   0 0 i-C.sub.3 H.sub.7                                                                           CH.sub.2 CH.sub.2 Cl                                                                       H   H      179-183                           63   0 0 i-C.sub.3 H.sub.7                                                                           CHCHCH.sub.3                                                                               H   H      157-160                           64   0 0 i-C.sub.3 H.sub. 7                                                                          C(CH.sub.3)CH.sub.2                                                                        H   H      156-159                           65   0 0 i-C.sub.3 H.sub.7                                                                           n-C.sub.3 H.sub.7                                                                          H   H      146-148.5                         66   0 0 i-C.sub.3 H.sub.7                                                                           C(CH.sub.3).sub.2 Br                                                                       H   H      151-153                           67   0 0 i-C.sub.3 H.sub.7                                                                           n-C.sub.5 H.sub.11                                                                         H   H      122-126                           68   0 0 i-C.sub.3 H.sub.7                                                                           CH(C.sub.2 H.sub.5).sub.2                                                                  H   H      157-158                           69   0 0 i-C.sub.3 H.sub.7                                                                           n-C.sub.6 H.sub.13                                                                         H   H      114-116                           70   0 0 i-C.sub.3 H.sub.7                                                                           benzyl      H   H      164-167                           71   0 0 CF.sub.3     CF.sub.3    H   H      207-211                           72   0 0 CH.sub.2 C(CH.sub.3).sub.3                                                                  C.sub.2 H.sub.5                                                                            H   H      177-179                           73   0 0 2,4-diCl-phenyl                                                                             C.sub.2 H.sub.5                                                                            H   H      210-212                           74   0 0 3,4-diCl-phenyl                                                                             C.sub.2 H.sub.5                                                                            H   H      175-177                           75   0 0 4-NO.sub.2 -phenyl                                                                          C.sub.2 H.sub.5                                                                            H   H      227-230                           76   0 0 CH.sub.2 C(CH.sub.3).sub.2                                                                  i-C.sub.3 H.sub.7                                                                          H   H      151-153                           77   0 0 2,4-diCl-phenyl                                                                             i-C.sub. 3 H.sub.7                                                                         H   H      186-188                           78   0 0 3,4-diCl-phenyl                                                                             i-C.sub.3 H.sub.7                                                                          H   H      189-191                           79   0 0 C(CH.sub.3).sub.2 C.sub.3 H.sub.7                                                           C.sub.2 H.sub.5                                                                            H   H      112-115                           80   0 0 CH(C.sub.2 H.sub.5)                                                                         C.sub.2 H.sub.5                                                                            H   H      153-157                           81   0 0 t-C.sub.4 H.sub.9                                                                           C.sub.2 H.sub.5                                                                            H   H      177-179                           82   0 0 CCl.sub.3    t-C.sub.4 H.sub.9                                                                          H   H      169-173                           83   0 0 C(CH.sub.3).sub.2 C.sub.3 H.sub.7                                                           t-C.sub.4 H.sub.9                                                                          H   H      119-120                           84   0 0 CF.sub.3     t-C.sub.4 H.sub.9                                                                          H   H      >300                              85   0 0 C(CH.sub.3).sub.2 C.sub.6 H.sub.13                                                          t-C.sub.4 H.sub.9                                                                          H   H      95-101                            86   0 0 C(CH.sub.3).sub.2 C.sub.6 H.sub.13                                                          C(CH.sub.3).sub.2 C.sub.6 H.sub.13                                                         H   H      94-98                             87   0 0 CCl.sub.2 CH.sub.3                                                                          CCl.sub.2 CH.sub.3                                                                         H   H      135.5-137.5                       88   0 0 CCl.sub.2 CH.sub.3                                                                          C.sub.2 H.sub.5                                                                            H   H      163-165                           89   0 0 CH.sub.2 C(CH.sub.3).sub.3                                                                  CH.sub.2 C(CH.sub.3).sub.3                                                                 H   H      187-190.5                         90   0 0 CCl.sub.3    CH.sub.2 C(CH.sub.2).sub.3                                                                 H   H      176-180                           91   0 0 CCl.sub.3    CH.sub.2 C(CH.sub.3).sub.3                                                                 H   H      177-180                           92   0 0 CF.sub.3     CH.sub.2 C(CH.sub.3).sub.3                                                                 H   H      200-201                           93   0 0 CCl.sub.2 CH.sub.3                                                                          CH.sub.2 C(CH.sub.3).sub.3                                                                 H   H      155.5-159                         94   0 0 C(CH.sub.3).sub.3                                                                           CH.sub.2 C(CH.sub.3).sub.3                                                                 H   H      184-185                           95   0 0 C(CH.sub.3).sub.2 C.sub.3 H.sub.7                                                           CH.sub.2 C(CH.sub.3).sub.3                                                                 H   H      105-110                           96   0 0 C(CH.sub.3).sub.2                                                                           C.sub.3 H.sub.7                                                                            H   H      133-134                           97   0 0 CF.sub.3     C(CH.sub.3).sub.2 C.sub.3 H.sub.7                                                          H   H      117-120                           98   0 0 CCl.sub.3    C(CH.sub.3).sub.2 C.sub.3 H.sub.7                                                          H   H      119-122                           99   0 0 C(CH.sub.3).sub.2 Br                                                                        C.sub.2 H.sub.5                                                                            H   H      144-147                           100  0 0 CHC(CH.sub.3).sub. 2                                                                        C.sub.2 H.sub.5                                                                            H   H      66-72                             101  0 0 CH(C.sub.2 H.sub.5).sub.2                                                                   C.sub.2 H.sub.5                                                                            H   H      155.5-156                         102  0 0 CH.sub.2 CH.sub.2 CH(CH.sub.3).sub.2                                                        C.sub.2 H.sub.5                                                                            H   H      127-130                           103  0 0 CH.sub.2 OCH.sub.3                                                                          CH.sub.2 C(CH.sub.3).sub.3                                                                 H   H      n.sub.D.sup.30 =1.5441            104  0 0 CHC(CH.sub.3).sub.2                                                                         CHC(CH.sub.3).sub.2                                                                        H   H      (glass)                           105  0 0 CHC(CH.sub.3).sub.2                                                                         C(CH.sub.3).sub.3                                                                          H   H      112-117                           106  0 0 CH.sub.2 CH.sub.2 CH(CH.sub.3).sub.2                                                        C(CH.sub.3).sub.3                                                                          H   H      109-112                           107  0 0 CHC(CH.sub.3).sub.2                                                                         C(CH.sub.3).sub.2 C.sub.3 H.sub.7                                                          H   H      (glass)                           108  0 0 CH.sub.2 CH(CH.sub.3)CH.sub.2 C(CH.sub.3).sub.3                                             C.sub.2 H.sub.5                                                                            H   H      108-111                           109  0 0 CH.sub.2 CH.sub.2 CH(CH.sub.3).sub.2                                                        CH.sub.2 CH.sub.2 CH(CH.sub.3).sub.2                                                       H   H      150-152                           110  0 0 CH.sub.2 CH.sub.2 CH(CH.sub.3).sub.2                                                        C(CH.sub.3).sub.2 H.sub.7                                                                  H   H      114-116                           111  0 0 CH.sub.2 CH(CH.sub.3)CH.sub.2 C(CH.sub.3).sub.3                                             C(CH.sub.3).sub.3                                                                          H   H      48-51                             112  0 0 CH.sub.2 CH(CH.sub.3)CH.sub.2 C(CH.sub.3).sub.3                                             C(CH.sub.3).sub.2 C.sub.3 H.sub.7                                                          H   H      (glass)                           113  0 0 CH(CH.sub.3)C.sub.2 H.sub.5                                                                 C.sub.2 H.sub.5                                                                            H   H      150-151                           114  0 0 CH(CH.sub.3)C.sub.2 H.sub.5                                                                 CH(CH.sub.3)C.sub.2 H.sub.5                                                                H   H      159-161                           115  0 0 CH(CH.sub.3)C.sub.2 H.sub.5                                                                 C(CH.sub.3).sub.3                                                                          H   H      169-171                           116  0 0 CH.sub.2 C(CH.sub.3).sub.3                                                                  CH(CH.sub.3)C.sub.2 H.sub.5                                                                H   H      146-149                           117  0 0 CF.sub.3     CH(CH.sub.3)C.sub.2 H.sub.5                                                                H   H      157-158                           118  0 0 2-Cl-phenyl  C.sub.2 H.sub.5                                                                            H   H      143.5-144.5                       119  0 0 4-Cl-phenyl  C.sub.2 H.sub.5                                                                            H   H      223-224.5                         120  0 0 2-CH.sub.3 O-phenyl                                                                         C.sub.2 H.sub.5                                                                            H   H      124-125                           121  0 0 4-CH.sub.3 O-phenyl                                                                         C.sub.2 H.sub. 5                                                                           H   H      223-224                           122  0 0 4-CH.sub.3 -phenyl                                                                          C.sub.2 H.sub.5                                                                            H   H      211-212                           123  0 0 4-Cl-phenyl  C(CH.sub.3).sub.3                                                                          H   H      191-195                           124  0 0 benzyl       C(CH.sub.3).sub.3                                                                          H   H      164-165                           125  0 0 benzyl       CH(CH.sub.3)C.sub.2 H.sub.5                                                                H   H      161-163                           126  0 0 benzyl       CH(CH.sub.3)C.sub.3 H.sub.7                                                                H   H      149.5-151                         127  0 0 benzyl       C(CH.sub.3).sub.2 C.sub.3 H.sub.7                                                          H   H      142-143.5                         128  0 0 styryl       C.sub.2 H.sub.5                                                                            H   H      160-163                           129  0 0 CH.sub.2 CH.sub.3                                                                           CH(CH.sub.3).sub.2                                                                         H   H 4'-Cl                                                                               161-162                           130  0 0 C(CH.sub.3).sub.3                                                                           CH(CH.sub.3).sub.2                                                                         H   H 4'-Cl                                                                               176.5-178.5                       131  0 0 CH.sub.2 C(CH.sub.3).sub.3                                                                  CH(CH.sub.3).sub.2                                                                         H   H 4'-Cl                                                                               194-194.5                         132  0 0 CCl.sub.3    CH(CH.sub.3).sub.2                                                                         H   H 4'-Cl                                                                               156-158                           133  0 0 benzyl       CH(CH.sub.3).sub.2                                                                         H   H 4'-Cl                                                                               211-212                           134  0 0 C.sub.2 H.sub.5                                                                             C.sub.2 H.sub.5                                                                            C.sub.2 H.sub.5                                                                    H      132-133                           135  0 0 CH.sub.2 C(CH.sub.3).sub.3                                                                  C.sub.2 H.sub.5                                                                            C.sub.2 H.sub.5                                                                    H      178.5-180                         136  0 0 CH.sub.2 OCH.sub.3                                                                          C(CH.sub.3).sub.3                                                                          H   H      108-109                           137  0 0 CH.sub.2 CH.sub.2 CH(CH.sub.3).sub.2                                                        C(CH.sub.3).sub.3                                                                          H   H      115-116                           138  0 0 CH.sub.2 CH.sub.2 CH(CH.sub.3).sub.2                                                        CH.sub.2 CH.sub.2 CH(CH.sub.3).sub.2                                                       H   H      151-153                           139  0 0 CH.sub.2 CH.sub.2 CH(CH.sub.3).sub.2                                                        C(CH.sub.3).sub.2 C.sub.3 H.sub.7                                                          H   H      121-123                           140  0 0 CH.sub.2 CH.sub.2 -phenyl                                                                   CH.sub.2 C(CH.sub.3).sub.3                                                                 H   H      101-107                           141  0 0 C.sub.2 H.sub.5                                                                             C.sub.2 H.sub.5 C(CH.sub.3).sub.3                                                          H   H      178-179                           142  0 0 CH.sub.2 CH.sub.2 C(CH.sub.3).sub.3                                                         CH(CH.sub.3)C.sub.3 H.sub.7                                                                H   H      75-77                             143  0 0 CH.sub.2 CH.sub.2 C(CH.sub.3).sub.3                                                         CH.sub.2 C(CH.sub.3).sub.3                                                                 H   H      184-185                           144  0 0 CH.sub. 2 CH.sub.2 C(CH.sub.3).sub.3                                                        CH.sub.2 CH.sub.2 C(CH.sub.3).sub.3                                                        H   H      216-218                           145  0 0 CH.sub.2 CH.sub.2 C(CH.sub.3).sub.3                                                         C(CH.sub.3).sub.2 C.sub.3 H.sub.7                                                          H   H      151-153                           146  0 0 C(CH.sub.3).sub.2 CH.sub.2 Cl                                                               C(CH.sub.3).sub.2 CH.sub.2 Cl                                                              H   H      145-150                           147  0 0 C(CH.sub.3).sub.2 CH.sub.2 Cl                                                               C.sub.2 H.sub.5                                                                            H   H      161-164                           148  0 0 C(CH.sub.3).sub.2 CH.sub.2 Cl                                                               C(CH.sub.3).sub.2 C.sub.3 H.sub.7                                                          H   H      110-112                           149  0 0 C.sub.2 H.sub.5                                                                             CH.sub.2 O-2,4-diCl-phenyl                                                                 H   H      206-207                           150  0 0 CH.sub.2 CHCH.sub.2                                                                         C.sub.2 H.sub.5                                                                            H   H      135-139                           151  0 0 CH.sub.2 CHCH.sub.2                                                                         CH.sub.2 CHCH.sub.2                                                                        H   H      99-108                            152  0 0 C(CH.sub.3)CH.sub.2                                                                         C(CH.sub.3).sub.3                                                                          H   H      159-166                           153  0 0 cyclopropyl  C(CH.sub.3).sub.3                                                                          H   H      176-178                           154  0 0 CH(CH.sub.3)C.sub.3 H.sub.7                                                                 C.sub.2 H.sub. 5                                                                           H   H      147-149                           155  0 0 C(CH.sub.3)C.sub.2 H.sub.5                                                                  C.sub.2 H.sub.5                                                                            H   H      141-144                           156  0 0 C.sub.3 H.sub.7 -n                                                                          C(CH.sub.3).sub.3                                                                          H   H      172-175                           157  0 0 CH.sub.2 CH(CH.sub.3).sub.2                                                                 C(CH.sub.3).sub.3                                                                          H   H      164.5-167                         158  0 0 n-C.sub.4 H.sub.9                                                                           C(CH.sub.3).sub.3                                                                          H   H      125-127                           159  0 0 C(CH.sub.3).sub.2 CH.sub.2 Cl                                                               C(CH.sub.3).sub.3                                                                          H   H      151-153                           160  0 0 CH.sub.2 CH.sub.2 cyclopentyl                                                               C.sub.2 H.sub.5                                                                            H   H      165- 166                          161  0 0 CH(C.sub.2 H.sub.5).sub.2                                                                   C(CH.sub.3).sub.3                                                                          H   H      168-170                           162  0 0 CH(CH.sub.3)C.sub.3 H.sub.7                                                                 C(CH.sub.3).sub.3                                                                          H   H      145-148                           163  0 0 CH(CH.sub.3).sub.2                                                                          C(CH.sub.3).sub.2 C.sub.3 H.sub.7                                                          H   H      115-120                           164  0 0 CH.sub.2 CH.sub.2 cyclohexyl                                                                C.sub.2 H.sub.5                                                                            H   H      154-155                           165  0 0 cyclohexyl   C(CH.sub.3).sub.3                                                                          H   H      187-188                           166  0 0 CH(CH.sub.3)C.sub.3 H.sub.7                                                                 CH(CH.sub.3)C.sub.3 H.sub.7                                                                H   H      111-115                           167  0 0 C(CH.sub.3).sub.2 C.sub.2 H.sub.5                                                           C(CH.sub.3).sub.2 C.sub.2 H.sub.5                                                          H   H      156-158                           168  0 0 pinonoyl     C.sub.2 H.sub.5                                                                            H   H      glass                             169  0 0 C(CH.sub.3).sub.2 C.sub.2 H.sub.5                                                           C(CH.sub.3).sub.2 C.sub.3 H.sub.7                                                          H   H      120.5-123                         170  0 0 CH(CH.sub.3)C.sub.3 H.sub.7                                                                 C(CH.sub.3).sub.2 C.sub.3 H.sub.7                                                          H   H      glass                             171  0 0 cyclohexyl   cyclohexyl  H   H      217-219                           172  0 0 cyclohexyl   C(CH.sub.3).sub.2 C.sub.3 H.sub.7                                                          H   H      153.5-157                         173  0 0 3-4-diCl-phenyl                                                                             C(CH.sub.3).sub.3                                                                          H   H      187-191                           174  0 0 CH.sub.2 O-2,4-diCl-phenyl                                                                  C(CH.sub.3).sub.3                                                                          H   H      163-165                           175  0 0 3,4-diCl-phenyl                                                                             C(CH.sub.3)C.sub.3 H.sub.7                                                                 H   H      107-114                           176  0 0 2,4-di-Cl-phenyl                                                                            C(CH.sub.3).sub.2 C.sub.3 H.sub.7                                                          H   H      153-157                           177  0 0 CH.sub.2 O-2,4-diCl-phenyl                                                                  C(CH.sub.3)C.sub.3 H.sub.7                                                                 H   H      126-129                           178  0 0 C(i-C.sub.3 H.sub.7).sub.2 CH.sub.3                                                         C.sub.2 H.sub.5                                                                            H   H      n.sub.D.sup.30 1.5225             179  0 0 CHCHCH.sub.3 C(CH.sub.3).sub.3                                                                          H   H      67-69                             180  0 0 CH.sub.2 CHCH.sub.2                                                                         C(CH.sub.3).sub.3                                                                          H   H      159-161                           181  0 0 CH.sub.2 CH.sub.2 cyclopentyl                                                               C(CH.sub.3).sub.3                                                                          H   H      142-143                           182  0 0 CH.sub.2 CH.sub.2 cyclohexyl                                                                C(CH.sub.3).sub.3                                                                          H   H      141.5-143                         183  0 0 3'-pinonyl   C(CH.sub.3).sub.3                                                                          H   H      61-67                             184  0 0 2,4-diCl-phenyl                                                                             C(CH.sub.3).sub.3                                                                          H   H      182-184                           185  0 0 C(i-C.sub.3 H.sub.7).sub.2 CH.sub.3                                                         C(CH.sub.3).sub.3                                                                          H   H      62-66                             186  0 0 CCl.sub.3    CH(CH.sub.3)C.sub.3 H.sub.7                                                                H   H      121-126                           187  0 0 CF.sub.3     CH(CH.sub.3)C.sub.3 H.sub.7                                                                H   H      139-146                           188  0 0 CH(CH.sub.3).sub.2                                                                          CH(CH.sub.3)C.sub.3 H.sub.7                                                                H   H      156-157                           189  0 0 CH(CH.sub.3)C.sub.2 H.sub.5                                                                 CH(CH.sub.3)C.sub.3 H.sub.7                                                                H   H      145-147                           190  0 0 C(CH.sub.3).sub.2 CH.sub.2 Cl                                                               CH(CH.sub.3)C.sub.3 H.sub.7                                                                H   H      n.sub.D.sup.30 1.5145             191  0 0 CH.sub.2 C(CH.sub.3).sub.3                                                                  CH(CH.sub.3)C.sub.3 H.sub.7                                                                H   H      n.sub.D.sup.30 1.5078             192  0 0 CH.sub.2 CH(CH.sub.3)CH.sub.2 C(CH.sub.3).sub.3                                             CH(CH.sub.3)C.sub.3 H.sub.7                                                                H   H      n.sub.D.sup.30 1.5020             193  0 0 CH.sub.2 O-2,4-diCl-phenyl                                                                  CH(CH.sub.3)C.sub.3 H.sub.7                                                                H   H      182.184                           194  0 0 C(CH.sub.3).sub.3                                                                           C(C.sub.2 H.sub.5).sub.2 CH.sub.3                                                          H   H      131-134.5                         195  0 0 CH.sub.2 C(CH.sub.3).sub.3                                                                  C(C.sub.2 H.sub.5).sub.2 CH.sub.3                                                          H   H      133-135                           196  0 0 CH.sub.2 CH(CH.sub.3)CH.sub.2 C(CH.sub.3).sub.3                                             C(C.sub.2 H.sub.5).sub.2 CH.sub.3                                                          H   H      57-62                             197  0 0 CH.sub.2 CH(CH.sub.3)C.sub.2 H.sub.5                                                        C.sub.2 H.sub.5                                                                            H   H      123-126                           198  0 0 CH.sub.2 CH(CH.sub.3)C.sub.2 H.sub.5                                                        C(CH.sub.3).sub.3                                                                          H   H      134-136                           199  0 0 CH.sub.2 CH(CH.sub.3)C.sub.2 H.sub.5                                                        CH(CH.sub.3)C.sub.3 H.sub.7                                                                H   H      107-108                           200  0 0 CH.sub.2 CH(CH.sub.3)C.sub.2 H.sub.5                                                        C(CH.sub.3).sub.2 C.sub.3 H.sub.7                                                          H   H      100-103                           201  0 0 CH.sub.2 CH(CH.sub.3)C.sub.2 H.sub.5                                                        CH.sub. 2 CH(CH.sub.3)C.sub.2 H.sub.5                                                      H   H      132-134                           202  0 0 CH(C.sub.2 H.sub.5)C.sub.4 H.sub.9                                                          C.sub.2 H.sub.5                                                                            H   H      126-129                           203  0 0 CH(C.sub.2 H.sub.5)C.sub.4 H.sub.9                                                          CH(C.sub.2 H.sub.5)C.sub.4 H.sub.9                                                         H   H      53-70                             204  0 0 CH.sub.2 C(CH.sub.3).sub.3                                                                  CH(CH.sub.3)CH.sub.3                                                                       H   H      189-192                           205  0 0 C.sub.2 H.sub.5                                                                             C(C.sub.2 H.sub.5).sub.2 CH.sub.3                                                          H   H      134-137                           206  0 0 CH(CH.sub.3)C.sub.3 H.sub.7                                                                 C(C.sub.2 H.sub.5).sub.2 CH.sub.3                                                          H   H      45-48                             207  0 0 CH.sub.2 C(CH.sub.3).sub.2 C.sub.2 H.sub.5                                                  C.sub.2 H.sub.5                                                                            H   H      174-175                           208  0 0 CH.sub.2 C(CH.sub.3).sub.2 C.sub.2 H.sub.5                                                  C(CH.sub.3).sub.3                                                                          H   H      156-157                           209  0 0 CH(C.sub.2 H.sub.5)C.sub.4 H.sub.9                                                          C(CH.sub.3).sub.3                                                                          H   H      132-134                           210  0 0 CH(C.sub.2 H.sub.5)C.sub.3 H.sub.7                                                          CH(CH.sub.3)C.sub.3 H.sub.7                                                                H   H      108-112                           211  0 0 CH(C.sub.2 H.sub.5)C.sub.4 H.sub.9                                                          C(CH.sub.3).sub.2 C.sub.3 H.sub.7                                                          H   H      119-121                           212  0 0 CH.sub.2 C(CH.sub.3).sub.2 C.sub.2 H.sub.5                                                  CH(CH.sub.3)C.sub.3 H.sub.7                                                                H   H      135-136                           213  0 0 CH.sub.2 C(CH.sub.3).sub.2 C.sub.2 H.sub.5                                                  C(CH.sub.3)C.sub.3 H.sub.7                                                                 H   H      108-110                           214  0 0 CH.sub.2 C(CH.sub.3).sub.2 C.sub.2 H.sub.5                                                  CH.sub.2 C(CH.sub.3).sub.2 C.sub.2 H.sub.5                                                 H   H      175-178                           215  0 0 C.sub.2 F.sub.5                                                                             C.sub.2 H.sub.5                                                                            H   H      172-175                           216  0 0 C.sub.2 F.sub.5                                                                             C(CH.sub.3).sub.3                                                                          H   H      187-190                           217  0 0 C.sub.2 F.sub.5                                                                             CH(CH.sub.3)C.sub.3 H.sub.7                                                                H   H      126-128                           218  0 0 C.sub.2 F.sub.5                                                                             C(CH.sub.3).sub.2 C.sub.3 H.sub.7                                                          H   H      112-114                           219  0 0 CCl.sub.2 CF.sub.3                                                                          C.sub.2 H.sub.5                                                                            H   H      141-143                           220  0 0 2-CH.sub.3 -phenyl                                                                          C(CH.sub.3).sub.3                                                                          H   H      185-186.5                         221  0 0 3-CH.sub.3 -phenyl                                                                          C(CH.sub.3).sub.3                                                                          H   H      163-164                           222  0 0 4-CH.sub.3 -phenyl                                                                          C(CH.sub.3).sub.3                                                                          H   H      206-207                           223  0 0 2-CH.sub.3 -phenyl                                                                          CH(CH.sub.3)C.sub.3 H.sub.7                                                                H   H      172-174                           224  0 0 3-CH.sub.3 -phenyl                                                                          CH(CH.sub.3)C.sub.3 H.sub.7                                                                H   H      68-72                             225  0 0 4-CH.sub.3 -phenyl                                                                          CH(CH.sub.3)C.sub.3 H.sub.7                                                                H   H      122-124                           226  0 0 2-CH.sub.3 -phenyl                                                                          C(CH.sub.3).sub.2 C.sub.3 H.sub.7                                                          H   H      154-155                           227  0 0 3-CH.sub.3 -phenyl                                                                          C(CH.sub.3).sub.2 C.sub.3 H.sub.7                                                          H   H      129-130                           228  0 0 4-CH.sub.3 -phenyl                                                                          C(CH.sub.3).sub.2 C.sub.3 H.sub.7                                                          H   H      146-148                           229  0 0 2-Cl-phenyl  C(CH.sub.3).sub.3                                                                          H   H      185-187                           230  0 0 3-Cl-phenyl  C(CH.sub.3).sub.3                                                                          H   H      193-194                           231  0 0 2-Cl-phenyl  CH(CH.sub.3)C.sub.3 H.sub.7                                                                H   H      154-156                           232  0 0 3-Cl-phenyl  CH(CH.sub.3)C.sub.3 H.sub.7                                                                H   H      118-120                           233  0 0 4-Cl-phenyl  CH(CH.sub.3)C.sub.3 H.sub.7                                                                H   H      131-133                           234  0 0 2-Cl-phenyl  C(CH.sub.3).sub.2 C.sub.3 H.sub.7                                                          H   H      128-130                           235  0 0 3-Cl-phenyl  C(CH.sub.3).sub.2 C.sub.3 H.sub.7                                                          H   H      132-133                           236  0 0 4-Cl-phenyl  C(CH.sub.3).sub.2 C.sub.3 H.sub.7                                                          H   H      135-137                           237  0 0 2-F-phenyl   C.sub.2 H.sub.5                                                                            H   H      186-187                           238  0 0 4-F-phenyl   C.sub.2 H.sub.5                                                                            H   H      205-206                           239  0 0 2-F-phenyl   C(CH.sub.3).sub.3                                                                          H   H      123-126                           240  0 0 4-F-phenyl   C(CH.sub.3).sub.3                                                                          H   H      195-196                           241  0 0 2-F-phenyl   CH(CH.sub.3)C.sub.3 H.sub.7                                                                H   H      129-131                           242  0 0 4-F-phenyl   CH(CH.sub.3)C.sub.3 H.sub.7                                                                H   H      141-143                           243  0 0 2-F-phenyl   C(CH.sub.3).sub.2 C.sub. 3 H.sub.7                                                         H   H      114-115                           244  0 0 4-F-phenyl   C(CH.sub.3).sub.2 C.sub.3 H.sub.7                                                          H   H      147-149                           245  0 0 CH(C.sub.2 H.sub.5).sub.2                                                                   CH(CH.sub.3)C.sub.3 H.sub.7                                                                H   H      157-159                           246  0 0 CH(CH.sub.3)C.sub.3 H.sub.7                                                                 CH(CH.sub.3)C.sub.3 H.sub.7                                                                H   H 3-Cl 63-66                             247  0 0 C.sub.2 H.sub.5                                                                             C.sub.2 H.sub.5                                                                            H   H 2-CH.sub.3                                                                          266-267                           248  0 0 i-C.sub.3 H.sub.7                                                                           i-C.sub.3 H.sub.7                                                                          H   H 2-CH.sub.3                                                                          295-296                           249  0 0 t-C.sub.4 H.sub.9                                                                           t-C.sub.4 H.sub.9                                                                          H   H 2-CH.sub.3                                                                          260-261                           250  0 0 CH(CH.sub.3)C.sub.3 H.sub.7                                                                 CH(CH.sub.3)C.sub.3 H.sub.7                                                                H   H 2-CH.sub.3                                                                          245-246                           251  0 0 C(CH.sub.3).sub.2 C.sub.3 H.sub.7                                                           C(CH.sub.3).sub.2 C.sub.3 H.sub.7                                                          H   H 2-CH.sub.3                                                                          176-177                           __________________________________________________________________________

Other examples of compounds falling within the generic formulas presented herein, which are preparable by the above described procedures and which may be formulated into herbicidal compositions and applied as herein illustrated are:

    ______________________________________                                         X   Y     R.sub.1     R.sub.2  R.sub.3                                                                             R.sub.4                                                                             Z                                     ______________________________________                                         O   S     H           H        H    H                                          O   S     C.sub.2 H.sub.5                                                                            H        H    H                                          O   S     C.sub.2 H.sub. 5                                                                           C.sub.2 H.sub.5                                                                         H    H                                          O   S     C.sub.2 H.sub.5                                                                            cyclopropyl                                                                             H    H                                          O   S     CH.sub.2 Cl CH.sub.2 Cl                                                                             H    H                                          O   S     cyclopropyl n-C.sub.5 H.sub.11                                                                      H    H                                          O   S     CH=CHCH.sub.3                                                                              C.sub.2 H.sub.5                                                                         H    H                                          O   S     furyl       furyl    H    H                                          O   S     CCl.sub.3   C.sub.2 H.sub.5                                                                         H    H                                          O   S     phenyl      phenyl   H    H                                          O   S     cyclohexyl  cyclohexyl                                                                              H    H                                          O   S     benzyl      C.sub.2 H.sub.5                                                                         H    H                                          O   S     2,4-diCl-phenyl                                                                            C.sub.2 H.sub.5                                                                         H    H                                          O   S     4-NO.sub.2 -phenyl                                                                         C.sub.2 H.sub.5                                                                         H    H                                          O   S     3,4-diCl-phenyl                                                                            i-C.sub.3 H.sub.7                                                                       H    H                                          O   S     C.sub.2 H.sub.5                                                                            CF.sub.3 H    H                                          O   S     t-C.sub.4 H.sub.9                                                                          t-C.sub.4 H.sub.9                                                                       H    H                                          O   S     phenyl      phenyl   H    H                                          O   S     cyclohexyl  cyclohexyl                                                                              H    H    5'-Cl                                 O   S     C.sub.2 H.sub.5                                                                            3-NO.sub.2 -phenyl                                                                      H    H                                          O   O     C.sub.2 H.sub.5                                                                            i-C.sub.3 H.sub.7                                                                       H    H    5'-Cl                                 O   O     C.sub.2 H.sub.5                                                                            i-C.sub.3 H.sub.7                                                                       H    H    5'-Br                                 O   O     C.sub.2 H.sub.5                                                                            i-C.sub.3 H.sub.7                                                                       H    H    5'-F                                  O   O     C.sub.2 H.sub.5                                                      C.sub.3 H.sub.7                                                                    H     H           5'-C.sub.2 H.sub.5                                       O   O     C.sub.2 H.sub.5                                                                            i-C.sub.3 H.sub.7                                                                       H    H    5'-NO.sub.2                           O   O     C.sub.2 H.sub.5                                                                            i-C.sub.3 H.sub.7                                                                       H    H    5'-CF.sub.3                           O   O     C.sub.2 H.sub.5                                                                            i-C.sub.3 H.sub.7                                                                       H    CH.sub.3                                   O   S     C.sub.2 H.sub.5                                                                            CH(C.sub.2 H.sub.5).sub.2                                                               H    CH.sub.3                                                                            5'-Cl                                 O   S     C.sub.2 H.sub.5                                                                            phenyl   H    CH.sub.3                                                                            5'-NO.sub.2                           O   O     CH.sub.2 C(CH.sub.3).sub.3                                                                 C.sub.2 H.sub.5                                                                         CH.sub.3                                                                            CH.sub.3                                   O   O     CH.sub.2 C(CH.sub.3).sub.3                                                                 C.sub.2 H.sub.5                                                                         CH.sub.3                                                                            H    5'-Cl                                 O   O     C.sub.2 H.sub.5                                                                            i-C.sub.3 H.sub.7                                                                       CH.sub.3                                                                            H    5'-CF.sub.3                           O   O     C(CH.sub.3).sub.2 C.sub.3 H.sub.7                                                          C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.5                                                                     CH.sub.3                                                                            5'-NO.sub.2                           O   S     C.sub.2 H.sub.5                                                                            i-C.sub.3 H.sub.7                                                                       CH.sub.3                                                                            CH.sub.3                                                                            5'-CH.sub.3                           O   O     H           H        H    H    5'-NH.sub.2                           O   O     C.sub.2 H.sub.5                                                                            C.sub.2 H.sub.5                                                                         H    H    5'-NH.sub.2                           O   O     C.sub.2 H.sub.5                                                                            i-C.sub.3 H.sub.7                                                                       CH.sub.3                                                                            CH.sub.3                                                                            5'-NH.sub.2                           O   S     H           H        CH.sub.3                                                                            CH.sub.3                                                                            5'-OCH.sub.3                          O   S     C.sub.2 H.sub.5                                                                            C.sub.2 H.sub.5                                                                         H    H    5'-OC.sub.2 H.sub.5                   S   O     C.sub.2 H.sub.5                                                                            i-C.sub.3 H.sub.7                                                                       CH.sub.3                                                                            CH.sub.3                                                                            5'-OCH.sub.3                          S   O     C.sub.2 H.sub.5                                                                            i-C.sub.3 H.sub.7                                                                       H    CH.sub.3                                                                            5'-NH.sub.2                           S   O     CH.sub.3    i-C.sub.3 H.sub.7                                                                       H    H    5'-OCH.sub.3                          S   S     C.sub.2 H.sub.5                                                                            C.sub.2 H.sub.5                                                                         CH.sub.3                                                                            CH.sub.3                                                                            5'-OCH.sub.3                          S   S     C.sub.2 H.sub.5                                                                            C.sub.2 H.sub.5                                                                         H    H    5'-NH.sub.2                           O   O     CH.sub.2 OC.sub.2 H.sub.5                                                                  C.sub.2 H.sub.5                                                                         H    H                                          O   O     C.sub.2 H.sub.4 OC.sub.2 H.sub. 5                                                          i-C.sub.3 H.sub.7                                                                       CH.sub.3                                                                            H                                          ______________________________________                                    

Pre-emergence herbicide test. On the day preceding treatment, seeds of seven different weed species are planted in individual rows using one species per row across the width of the flat. The seeds used are hairy crabgrass (Digitaria sanguinalis (L.) Scop.), yellow foxtail (Setaria glauca (L.) Beauv.), watergrass (Echinochloa crusgalli (L.) Beauv.), California read oat (Avena sativa (L.)), redroot pigweed (Amaranthus retroflexus (L.), Indian mustard (Brassica juncea (L.) Coss.) and curly dock (Rumex crispus (L.). Ample seeds are planted to give about 20 to 50 seedlings per row, after emergence, depending on the size of the plants. The flats are watered after planting. The spraying solution is prepared by dissolving 50 mg. of the test compound in 3 ml. of a solvent, such as acetone, containing 1% Tween 20® (polyoxyethylene sorbitan monolaurate.) The following day, each flat is sprayed at the rate of 20 pounds of the candidate compound per 80 gallons of solution per acre. An atomizer is used to spray the solution on soil surface. The flats are placed in a greenhouse at 80° F. and watered regularly. Two weeks later, the degree of weed control is determined by comparing the amount of germination and growth of each weed in the treated flats with weeds in several untreated control flats.

The rating system is as follows:

- = no significant injury (0-15 percent control)

+ = slight injury (25-35 percent control)

++ = moderate injury (55-65 percent control)

+++ = severe injury or death (85-100 percent control) An activity index is used to represent the total activity on all seven weed species. It is the sum of the number of plus marks, so that an activity index of 21 represents complete control of all seven weeds. The results of this test are reported in Table II.

Post-emergence Herbicide Test

Seeds of five weed species including hairy crabgrass, watergrass, wild oats, Indian mustard, and curly lb/acre. and one crop pinto beans (Phaseolus vulgaris), are planted in flats as described above for pre-emergence screening. The flats are placed in the greenhouse at 72°-85° F. and watered daily with a sprinkler. About 10 to 14 days after planting when the primary leaves of the bean plant are almost fully expanded and the first trifoliate leaves are just starting to form, the plants are sprayed. The spray is prepared by weighing out 50 mg. of the test compound, dissolving it in 5 ml. of acetone containing 1 percent Tween 20® (polyoxy-ethylene sorbitan monolaurate) and then adding 5 ml. of water. The solution is sprayed on the foliage using an atomizer. The spray concentration is 0.5% and the rate would be approximately 20 lb/acre if all of the spray were retained on the plant and the soil, but some spray is lost so it is estimated that the application is approximately 12.5 lb/acre.

Beans are used to detect defoliants and plant growth regulators. The beans are trimmed to two or three plants per flat by cutting off the excess weaker plants several days before treatment. The treated plants are placed back in the greenhouse and care is taken to avoid sprinkling the treated foliage with water for three days after treatment. Water is applied to the soil by means of a slow stream from a watering hose taking care not to wet the foliage.

Injury rates are recorded 14 days after treatment. The rating system is the same as described above for the preemergence test where (-), (+), (++), and (+++) are used for the different rates of injury and control. The injury symptoms are also recorded. The maximum activity index for complete control of all the species in the post-emergence screening test is 18 which represents the sum of the plus marks obtained with the six plant species used in the test. The herbicide activity index is shown in Table II.

                  TABLE II                                                         ______________________________________                                         HERBICIDAL ACTIVITY ** - SCREENING RESULTS                                     Compound                                                                       Number     Pre-emergence  Post-emergence                                       ______________________________________                                         1          12             15                                                   2          2              12                                                   3          7              3                                                    4          1              0                                                    5          0              5                                                    6          9              5                                                    7          18             15                                                   8          15             18                                                   9          0              7                                                    10         0              8                                                    11         19             18                                                   12         11             16                                                   13         20             18                                                   14         17             15                                                   15         14             18                                                   16         0              13                                                   17         1              8                                                    18         0              9                                                    19         0              7                                                    20         0              10                                                   21         12             16                                                   22         12             15                                                   23         6              13                                                   24         6              12                                                   25         4              8                                                    26         8              9                                                    27         11             16                                                   28         9              14                                                   29         17             15                                                   30         21             17                                                   31         2              11                                                   32         0              8                                                    33         0              9                                                    34         9              16                                                   35         2              9                                                    36         9              15                                                   37         6              14                                                   38         20             18                                                   39         6              12                                                   40         11             12                                                   41         5              14                                                   42         10             12                                                   43         9              12                                                   44         8              18                                                   45         18             16                                                   46         8              11                                                   47         8              12                                                   48         6              12                                                   49         16             18                                                   50         5              12                                                   51         5              11                                                   52         6              12                                                   53         6              0                                                    54         12             12                                                   55         21             18                                                   56         19             17                                                   57         6              8                                                    58         0              2                                                    59         10             9                                                    60         21             18                                                   61         15             16                                                   52         7              12                                                   63         16             16                                                   64         14             15                                                   65         3              10                                                   66         20             17                                                   67         8              8                                                    68         21             18                                                   69         0              11                                                   70         14             15                                                   71         10             11                                                   72         21             18                                                   73         11             12                                                   74         12             11                                                   76         20             18                                                   77         12             15                                                   78         3              11                                                   79         21             18                                                   80         18             18                                                   81         19             18                                                   82         17             16                                                   83         18             18                                                   84         7              12                                                   85         6              7                                                    86         0              2                                                    87         19             16                                                   88         21             18                                                   89         9              12                                                   90         0              3                                                    91         11             16                                                   92         4              10                                                   93         8              18                                                   94         20             18                                                   95         19             18                                                   96         18             18                                                   97         11             18                                                   98         6              14                                                   99         19             18                                                   100        13             18                                                   101        19             18                                                   102        6              15                                                   103        12             18                                                   104        19             18                                                   105        20             18                                                   106        14             17                                                   107        17             18                                                   108        11             18                                                   109        6              12                                                   110        12             17                                                   111        12             18                                                   112        9              14                                                   113        21             18                                                   114        19             18                                                   115        20             18                                                   116        21             18                                                   117        5              18                                                   118        11             17                                                   119        9              14                                                   120        5              14                                                   121        0              1                                                    122        0              12                                                   123        12             17                                                   124        17             18                                                   125        10             18                                                   126        9              18                                                   127        15             18                                                   128        3              17                                                   129        9              16                                                   130        7              9                                                    131        7              11                                                   132        16             15                                                   133        8              9                                                    134        6              14                                                   135        6              11                                                   136        12             13                                                   137        14             15                                                   138        2              13                                                   139        14             14                                                   140        0              7                                                    141        14             18                                                   142        12             16                                                   143        5              12                                                   144        0              2                                                    145        6              12                                                   146        3              4                                                    147        21             18                                                   148        21             17                                                   149        8              12                                                   150        10             17                                                   151        7              16                                                   152        15             17                                                   153        16             18                                                   154        18             18                                                   155        16             18                                                   156        17             19                                                   157        19             17                                                   158        11             16                                                   159        15             14                                                   160        3              11                                                   161        19             18                                                   162        21             18                                                   163        21             18                                                   164        0              8                                                    165        9              16                                                   166        18             18                                                   167        11             13                                                   168        9              15                                                   169        21             17                                                   170        20             18                                                   171        0              0                                                    172        0              14                                                   173        0              15                                                   174        17             15                                                   175        8              16                                                   176        9              14                                                   177        9              16                                                   178        9              18                                                   179        18             18                                                   180        19             18                                                   181        2              12                                                   182        0              9                                                    183        6              8                                                    184        14             12                                                   185        13             9                                                    186        14             15                                                   187        19             18                                                   188        21             16                                                   189        20             16                                                   190        21             18                                                   191        21             18                                                   192        9              12                                                   193        5              10                                                   194        18             11                                                   195        13             9                                                    196        1              4                                                    197        20             16                                                   198        21             16                                                   199        21             15                                                   200        21             16                                                   201        19             14                                                   202        21             18                                                   203        0              6                                                    204        10             11                                                   205        21             17                                                   206        21             15                                                   207        18             18                                                   208        17             15                                                   209        13             17                                                   210        13             18                                                   211        6              13                                                   212        16             14                                                   213        13             5                                                    214        0              4                                                    215        20             18                                                   216        16             18                                                   217        15             18                                                   218        16             18                                                   219        17             18                                                   220        4              11                                                   221        7              14                                                   222        0              4                                                    223        3              11                                                   224        8              12                                                   225        2              14                                                   226        7              14                                                   227        9              15                                                   228        0              10                                                   229        11             10                                                   230        6              10                                                   231        8              12                                                   232        8              12                                                   233        5              11                                                   234        9              13                                                   235        9              14                                                   236        6              12                                                   237        7              6                                                    238        11             10                                                   239        15             16                                                   240        8              9                                                    241        9              11                                                   242        8              12                                                   243        10             14                                                   244        6              11                                                   245        19             18                                                   246        0              14                                                   247        6              5                                                    248        0              5                                                    249        5              5                                                    250        3              4                                                    251        6              7                                                    ______________________________________                                    

21= 85-100% control of all seven plant species tested preemergence.

18= 85-100% control of all six plant species tested postemergence.

The compounds of the present invention are used as pre-emergence of post-emergence herbicides and are applied in a variety of ways at various concentrations. In practice, the compounds are formulated with an inert carrier, utilizing methods well-known to those skilled in the art, thereby making them suitable for application as dusts, sprays, or drenches and the like in the form and manner required. The mixtures can be dispersed in water with the aid of a wetting agent or they can be employed in organic liquid compositions, oil and water, water in oil emulsions, with or without the addition of wetting, dispersing or emulsifying agents. The amount applied depends upon the nature of the seeds or plants to be controlled and the rate of application varies from approximately 1 to approximately 50 pounds per acre. One particularly advantageous way of applying the compound is a narrow band along a row crop straddling the row. In practice, the compounds are formulated with an inert carrier utilizing methods well known to those skilled in the art, thereby making them suitable for particular application.

The phytotoxic compositions of this invention are applied to the plants in the conventional manner. Thus, the dust and liquid compositions can be applied to the plant by the use of power-dusters, boom and hand sprayers and spray-dusters. The compositions can also be applied from airplanes as a dust or a spray because they are effective in very low dosages. In order to modify or control growth of germinating seeds or emerging seedlings, as a typical example, the dust and liquid compositions are applied to the soil according to conventional methods and are preferably distributed in the soil to a depth of at least 1/2-inch below the soil surface. It is not necessary that the phytotoxic compositions be admixed with the soil particles and these compositions can be applied merely by spraying or sprinkling the surface of the soil. The phytotoxic compositions of this invention can also be applied by addition to irrigation water supplied to the field to be treated. This method of application permits the penetration of the compositions into the soil as the water is absorbed therein. Dust compositions, granular compositions or liquid formulations applied to the surface of the soil can be distributed below the surface of the soil by conventional means such as discing, dragging or mixing operations.

The phytotoxic compositions of this invention can also contain other additaments, for example fertilizers, pesticides and the like, used as adjuvant or in combination with any of the above-described adjuvants. Other phytotoxic compounds useful in combination with the above-described compounds include for example 2,4-dichlorophenoxyacetic acids 2,4,5-trichlorophenoxyacetic acid, 2 - methyl - 4-chlorophenoxyacetic acid and the salts, esters and amides thereof; triazine derivatives, such as 2,4-bis (3-methoxypropylamino)-6-methylthio-S-triazine; 2-chloro-4-ethylamino-6-isopropylamino-S-triazine, and 2-ethylamino-4-isopropylamino-6-methylmercapto-S-triazine, urea derivatives, such as 3-(3,4-dichlorophenyl)-1,1-dimethyl urea and 3-(p-chlorophenyl)-1,1-dimethyl urea and acetamides such as N,N - dially -α -chloroacetamide, N-(α -chloroacetayl)hexamethylene imine, and N,N-diethyl-a-bromacetamide and the like; benzoic acids such as 3-amino-2,5-dichlorobenzoic and; thiocarbamates, such as S-propyl dipropylthiocarbamate; S-ethyl-dipropylthiocarbamate, S-ethyl-cyclohexylethyl-thiocarbamate, S-ethyl hexahydro-1H-azepine-1-carbothioate and the like. Fertilizers useful in combination with the active ingredients include for example ammonium nitrate, urea and superphosphates. Other useful additaments include materials in which plant organisms take root and grow such as compost, manure, humus, sand and the like.

The concentration of a compound of the present invention, constituting an effective amount in the best mode of administration in the utility disclosed is readily determinable by those skilled in the art. Various changes and modifications are possible without departing from the spirit and scope of the invention described herein and will be apparent to those skilled in the art to which it pertains. It is accordingly intended that the present invention shall only be limited by the scope of the claims. 

What is claimed is:
 1. A method for controlling the growth of vegetation which comprises applying to the area where control of said vegetative growth is desired, a growth controlling amount of a compound having the formula ##STR5## in which X and Y are each oxygen, R₃ and R₄ are each hydrogen, R₂ is halogenated lower alkyl and R₁ is alkyl containing from 1 through about 10 carbon atoms, inclusive, and n is
 0. 2. The method according to claim 1 in which R₁ is ethyl and R₂ is 1-bromo-1-methyl ethyl.
 3. The method according to claim 1 in which R₁ is isopropyl and R₂ is trichloromethyl.
 4. The method according to claim 1 in which R₁ is isopropyl and R₂ is 1-chloroethyl.
 5. The method according to claim 1 in which R₁ is isopropyl and R₂ is 1-bromo-1-methyl ethyl.
 6. The method according to claim 1 in which R₁ is ethyl and R₂ is trifluoromethyl.
 7. The method according to claim 1 in which R₁ is ethyl and R₂ is 1,1-dichloroethyl.
 8. The method according to claim 1 in which R₁ is ethyl and R₂ is 1,1-dimethyl-2-chloroethyl. 